The present invention relates to a process for preparing carboxylic esters by reaction of a reaction mixture comprising a carboxylic acid and/or a carboxylic anhydride and an alcohol.
Esters of phthalic acid, adipic acid, sebacic acid or maleic acid are widely employed in surface coating resins, as constituents of paints and in particular as plasticizers for plastics.
It is known that carboxylic esters can be prepared by reacting carboxylic acids with alcohols. This reaction can be carried out autocatalytically or catalytically, for example in the presence of Brönsted or Lewis acids as catalysts. Regardless of the type of catalysis, there is always a temperature-dependent equilibrium between the starting materials (carboxylic acid and alcohol) and the products (esters and water).
The reaction of internal carboxylic anhydrides with alcohols proceeds in two steps: the alcoholysis of the anhydride to form the monoester generally proceeds rapidly and to completion. The further conversion of the monoester into the diester with formation of water of reaction is reversible and proceeds slowly. This second step is the rate-determining step of the reaction.
To shift the equilibrium in the direction of the ester (or the full ester in the case of polybasic acids), it is usual to use an entrainer by means of which the water of reaction is removed from the mixture. If one of the starting materials (alcohol or carboxylic acid) has a boiling point lower than that of the ester formed and forms a miscibility gap with water, a starting material can be used as entrainer and be recirculated to the mixture after water has been separated off. In the esterification of higher aliphatic carboxylic acids, aromatic carboxylic acids or dibasic or polybasic carboxylic acids, the alcohol used is generally the entrainer. If the alcohol used serves as entrainer, it is usual to condense at least part of the vapor from the reactor, separate the condensate into an aqueous phase and an organic phase comprising essentially the alcohol used for the esterification and recirculate at least part of the organic phase to the reactor.
EP-A 1 186 593 describes a process for preparing carboxylic esters by reacting dicarboxylic or polycarboxylic acids or anhydrides thereof with alcohols, with the water of reaction being removed by azeotropic distillation with the alcohol. The amount of liquid removed from the reaction by the azeotropic distillation is replaced either completely or partly by the alcohol.
In Chemie-Ing.-Technik 41 (1969), No. 17, pp. 971-974, H. Suter describes the continuous preparation of phthalic esters in a cascade of stirred vessels.
The prior art comprises various proposals for improving the removal of the water of reaction.
Thus, EP 680 463 B1 describes a process for esterifying acids or acid anhydrides with a monoalcohol or a polyhydroxy compound, in which a reaction mixture is heated to boiling and water is removed as vapor and the reaction mixture is mixed continuously so that at least 2.5 volumes of reaction mixture are circulated internally per minute. The mixing under the stated conditions is said to increase the degree of conversion.
EP-A 835 860 relates to a process for separating off water from reaction mixtures for the esterification of acids or acid anhydrides with alcohols at the boiling point of the reaction mixture, in which the lowest-boiling starting material is firstly used in a substoichiometric amount, the resulting vapor mixture composed of predominantly water and the lowest-boiling component is dewatered over a membrane, the dewatered vapor mixture is recirculated to the reaction mixture and further amounts of the lowest-boiling starting material are added to the reaction mixture during the course of the reaction.